Liquid detergent compositions

ABSTRACT

948,240. Liquid detergent compositions. PROCTER &amp; GAMBLE CO. May 25, 1962 [May 27, 1961], No. 20227/62. Heading C5D. An aqueous non-alcoholic detergent composition comprises by weight (a) 20-40% of a mixture of (i) one or more C9-18-alkyl benzene sulphonates, preferably sodium dodecylbenzene sulphonate, and (ii) one or more C10-18-alkyl polyoxyethylene sulphates having 2-4 ethylene oxide units in the molecule, preferably coconut alcohol tri-(oxyethylene) sulphate, the cations present in (i) and (ii) being sodium and/or potassium and/or ammonium and the weight ratio of (i) to (ii) being preferably 0.5: 1 to 3 : 1 and most suitably about 1:1; (b) 0.5-5% of a C10-16-fatty acyl alkanolamide, preferably coconut monoethanolamide; (c) 6-18% of sodium and/or potassium and/or ammonium toluene and/or xylene sulphonates, a 2:1 mixture by weight of potassium toluene sulphonate and sodium xylene sulphonate being preferred; and (d) the balance being substantially water. Perfume, colour, optical bleach, anti-tarnish agents, opacifiers, oxidizing agents and buffers may also be present.

United States Patent 3,231,504 LIQUHD DETERGENT CORFQSITIONS George Francis Marion, Paramus, Theodore Leo Treitler,

Miilburn, and Peter Arthur Manger, Nutley, NJ., as-

signors to Colgate-Palmolive Company, New York,

N.Y., a corporation of Delaware No Drawing. Filed Mar. 31, 1961, $er. No. 99,696

7 Qlaims. (Ql. 252137) The present invention relates to a liquid detergent composition comprising in combination a higher alkyl aryl sulfonate detergent, a higher alkyl polyethoxarner sulfate detergent, a potassium polyphosphate salt and a sulfonated solubilizing or hydrotropic agent in an aqueous medium, as hereinafter described and claimed.

More particularly, it has been found that a liquid detergent composition of superior qualities can be formulated which comprises essentially about to 18% by weight of a mixture of an alkali metal higher alkyl mononuclear aryl sulfonate salt, said higher alkyl group having about 8 to carbon atoms, an alkali metal higher alkyl polyethoxamer sulfate salt material, said higher alkyl group having about 10 to 18, preferably 12 to 14 carbon atoms and said polyethoxarner sulfate material having an average of about 2 to about 15, preferably 3 to 8, moles of ethylene oxide, the ratio of said alkyl aryl sulfonates to polyethoxamer sulfate being from about 6.5:1 to about 1:4 by weight; a total of about if) to by weight of water-soluble inorganic builder salts comprising primarily potassium polyphosphate and about 6 to 12% by weight of a water-soluble sulfonated hydrotropic salt in an aqueous solubilizing medium. Various other distinctive aspects of the present invention will be apparent from the following description.

The liquid containing the above ingredients in solution exhibits many desirable characteristics with regard to both physical properties and performance in use. As to its physical properties, it is a homogeneous, pourable, clear liquid as manufactured and after aging at room temperature. It exhibits a high degree of stability upon storage at normal room temperature of the order of about 70 F. over a period of many months without any appreciable precipitation or formation of immiscible layers. it can be subjected to elevated temperatures of the order of 120 F. or cooled to 40 F. and the liquid is in a clear, homogeneous form when returned to room temperature. As a result, the consumer can utilize it conveniently by the addition of small portions to a dishpan or a laundering bath and the detergent and builder salts will be present in constant composition in each portion. While adjuvant materials may be added which render the final product translucent or opaque as desired and described hereinafter, a clear solution of the main ingredients insures that effective foam and washing power will be obtained with each portion and pro motes the stability and homogeneity of the product. The liquid may be employed in any suitable container or packaging material such as metal, plastic, or glass in the form of bottles, bags, cans or drums.

in performance, the product exhibits a particularly high level of washing power and desired foaming action during dishwashing, laundering and in other cleansing operations. A particular advantage of this composition is its high detergent and emulsification power for the cleanin of soiled surfaces containing fats and greases including soiled aluminum and other metals, ceramic materials, Wearing apparel and the like. The product exhibits a good volume of foam initially and during the cleansing operation. Optimum effects, particularly in foaming, are achieved with compositions containing the Patented Jan. 25, 1966 alkyl polyethoxamer sulfates having 12 to 14 carbons in the alkyl group.

In the formulation of the product of the present invention, there are a number of factors which are of consideration. The properties are affected by these factors which are properly selected and correlated to provide the product hereafter claimed. Among such considerations are the chemical constitution of the materials which are to be integrated with the suitable ratios and/ or proportions thereof so as to produce compositions having the desired properties.

With regard to the higher alkyl mononuclear aryl sulfonate detergent, it is preferred to use the higher alkyl benzene sulfonates, though other similar detergents having a mononuclear aryl group derived from toluene or Xylene may be used also. The aryl nucleus has at least one alkyl substituent having an average number of about 8 to 15 carbons and preferably between 12 and 15 carbons. The alkyl group may be branched such as nonyl, dodecyl and pentadecyl groups including mixtures thereof which are derived from polymers of mono-olefins, e.g., polypropylene. Alternatively, the alkyl group may be traight-chained such as the decyl, keryl and dodecyl groups.

The suitable sulfated higher alkyl poiyethoxamer material has a characteristic chemical structure also. In general, the higher alkyl group has an average number of about 10 to 18, preferably 12 to 14 carbon atoms, which can be straight or branched chained also. Suitable examples are n-decyl, nand branched dodecyl, and tetradecyl groups; the ranched tridecyl and similar groups derived from olefins by the OX0 process; and mixed alkyl groups from fatty alcohols derived from reduction of fatty acids of coconut oil, tallow, hydrogenated coconut oil, and the like. It has a pro-determined number of ethylene oxide groups in order to obtain the desired physical properties and performance characteristics. In general, the polyethoxamer has an average number of 2 to 15 moles of ethylene oxide per alkyl group, preferably about 3 to 8 moles for Optimum effects.

The polyethoxamer sulfate material is commonly prepared by reaction of the appropriate aliphatic alcohol with sufficient ethylene oxide followed by sulfation of the reaction product in known manner, such as by the use of ole-um or chlorsulfonic acid. If desired, the polyethoxamer may be sulfated during or after the sulfonation of the alkyl aryl hydrocarbon using the same sulfonating agent to produce the mixed detergents.

The described alkyl aryl sulfonate and sulfa-ted alkyl polyethoxamer materials are employed in the form of their alkali metal salts such as the sodium and potassium salts. It is understood that there may be small amounts of inorganic salts such as sodium or potassium sulfate in the sulfonated and sulfated detergents resulting from the method of manufacture. In general, these inorganic sulfate salts should be maintained at as low a concentration as practicable.

The potassium polyphosphate salts have the property of inhibiting precipitation .of calcium and magnesium material in aqueous solution and of contributing to the heavy-duty performance of the liquid detergent product in washing operations. While they may be considered as derived from orthophosphoric acid or the like by the removal of molecularly bound water, any suitable means of manufacture may be employed if desired. Such complex or molecularly dehydrated polyphosphate salts are used usually in the form of the normal or completely neutralized salts, e.g., tetrapotassium pyrophosphate and pentapotassium tripolyphosphate. If desired, the phosphate may be a partially neutralized salt, e.g., potassium acid tripolyphosphate. Any suitable mixture of polyphosphate materials may be employed. It is preferred to use at least in part tetrapotassium pyrophosphate.

The organic detergents and polyphosphate are employed in substantial amount in the composition such that the addition of a small portion of the liquid product to a washing bath will result in effective detergency and washing power. The amount and types of said mixture of organic detergents influence the maximum amount of phosphate that can be dissolved in the composition and yet obtain a composition with the desired properties. Suitable amounts within the range of about 10 to 18%, by weight, preferably 14 to 16%, of said mixture of detergents and 10 to 20% by weight of potassium polyphosphate may be selected so as to produce suitable products. The ratio of the alkyl benzene sulfonate to the sulfated polyethoxamer is variable and ratios selected from the range of 6.5:1 to about 1:4 by weight have been found to be most practicable. It is preferred that the ratio of alkyl aryl sulronate to sulfated polyethoxamer be greater than 1:1, and particularly from about 1.5:1 to about 3:1 for optimum performance characteristics, particularly in foaming power. As a general guiding principle, it is advisable to vary the detergent and polyphosphate contents inversely, i.e., relatively low amounts of one are used when relatively high amounts of the other are desired in the product. Other water-soluble inorganic builder salts may be substituted for the potassium polyphosphate in minor amount such as a few percent, e.g., up to 5% of sodium polyphosphate or sodium or potassium silicate provided that the builder content is primarily the Potassium polyphosphate, e.g., at least about and the total amount is compatible in the liquid.

In the alkyl polyethoxamer sulfate materials, the average number of ethylene oxide groups and character of the alkyl group influences the physical properties of the liquid'and the amount of inorganic salt, particularly the amount of potassium polyphosphate, which can be dissolved in the solution. For example, a series of liquid detergents are prepared which contain about 7% by weight of sodium commercial tridecyl benzene sulfonate, 7% by weight of sodium higher alkyl ethylene oxide sulfates, 8% sodium commercial xylene sulfonate, 3% coconut isopropanolamide, and a quantity of potassium pyrophosphate in water. Each formulation contains a different polyethoxamer sulfate having the alkyl group and average ethylene oxide content as specified in the table below. The tridecyl group is a branched-chain alkyl group derived from olefins by the Oxo process and the tallow groups are derived from reduction of tallow fatty acids. The compositions contain the indicated amount of potassium pyrophosphate which is the' approximate maximum normally dissolved in each of the specified formulations. The cloud point after manufacture and the clear point after overnight aging at 40 F., for each composition are set forth in the table also.

The above data illustrate the desirability of selecting particular polyethoxame-r sulfates in order to obtain the best combination of properties in the liquid compositions. The sulfated tridecyl alcohol exhibited unsatisfactory physical properties in the composition compared to the sulfated polyethoxamers which exhibited satisfactory cloud and clear points. It is apparent also that the amount of polyphosphate which can be dissolved or tolerated in said solutions is decreased as the ethylene oxide content is increased to 10 moles or more in each alkyl polyethoxamer.

The inclusion of the water-soluble sulfonated hydrotropic substance is effective in promoting the compatibility of the ingredients so as to form a homogenous liquid product. Suitable materials are the alkali metal organic sulfonated (including sulfated) salts having a lower alkyl group up to about 6 carbons. It is preferred to employ an alkyl .aryl sulfonate having up to '3 carbons in a lower alkyl group such as the sodium and potassium xylene, toluene, ethylbenzene and isopropyl benzene sul-' fonates. Sulfonates made from xylene include orthoxylene sulfonate, metaxylene sulfonate, paraxylene sulfonate and ethylbenzene sulfonate. Commercial xylene sulfonates usually contain metaxylene sulfonate as the main ingredient. Analysis of typical commercial products show about 40-50% metaxylene sulfonate, 10-35% orthoxylene sulfonate and 15-30% paraxylene sulfonate with 0-20% ethylbenzene sulfonate. Any suitable isomeric mixture may be employed, however. Suitable lower alkyl sulfate salts having about 5 to 6 carbons in the alkyl group may be employed also such as the alkali metal n-amyl and n-hexyl sulfates. The hydrotropic materials are employed generally in amounts from about 6 to 12% by weight of the composition. The

' use of an amount in excess of the amount required to effect a single liquid phase is not helpful since it tends to add additional salt to an already concentrated system.

It is preferred that the liquid contain a higher fatty acid alkylolamide material in a sufiicient amount to act as a suds builder. It has been found also that combination of the above ingredients with a suitable amount of the alkylolamide results in a product which exhibits particularly high foaming power in use, particularly in the stability of the foam generated during dishwashing or laundering operations. In certain formulations, the alky1olamide may provide an additional solubilizing effect. It should not be employed in an amount sufiicient to destroy the desired physical properties since it is considered as part of the total solids content. The acyl radical of the alkylolamide is selected from the class of fatty acids having 8 to 18 carbons and each alkylol group has up to 3 carbon atoms usually. Itis preferred to use the diethanolamides, isopropanolamides and monoethanolamides of fatty acids having about 10 to 14 carbons in the acyl radical. Examples are the lauric, capric, myristic and coconut diethanolamides, monoethanolarnides and isopropanolamides, and mixtures thereof. There may be employed also the alkylolamides which are substituted by additional alkylolgroups, suitable examples being the above monoethanolamides, diethanolamides and isopropanolamides condensed with one or two moles of ethylene oxide. In general, the alkylolamides should be employed in amounts of about 2 to 10% by weight in the product, and preferably from about 4 to 8%.

The solids content of the concentrated liquid product is variable and is usually from about 26 to 50% by weight of the concentrated liquid, and the balance being pri marily water. The ingredients are proportioned in theaqueous solubilizing medium so as to form a substantially homogenous product of desired physical properties.

A minor amount of a water-soluble saturated aliphatic monohydric alcohol of 2 to 3 carbon atoms may be employed as part of the aqueous solubilizing medium. Examples are ethanol, propanol and isopropanol. The alcohol may serve a multiplicity of functions. It can provide for improved physical properties such as a lower cloud point, improve low temperature aging, modify the viscosity, and the like- In certain cases, a small amount of alcohol in combination with the hydrotropic salt produces a clear liquid which will be otherwise cloudy at room temperature. The suitable amount of alcohol which may be employed varies with the particular formulation. In general, the amount of alcohol employed is up to about 3% by weight of the composition, preferably from about 0.1 to 2% by weight, depending upon the etfects desired.

A suitable soil-suspending material may be incorporated in these formulations. The. addition of a soilsuspending material converts the system to a more complex one which has improved performance characteristics in washing operations and will usually render the final product translucent or opaque, though the detergent and builder salts are advantageously in solution. In general, the soil-suspending agent is a hydrophilic colloid which is dispersible in water and is maintained in suspension in the liquid product. It is preferred to use the alkali metal salt of a carboxy lower alkyl cellulose having up to 3 carbons in the alkyl group, such as the sodium and potassium salt of carboxymethylcellulose. The commercial grade of sodium carboxymethylcellulose and the like may be employed. Other known watersoluble cellulosic materials are the lower alkyl and hydroxy alkyl ethers such as methylcellulose, ethyleellulose and hydroxyethylcellulose; and the various cellulose sulfate materials.

Other types of soil-suspending agents may be employed such as the water-soluble vinyl polymers. are water-soluble polyvinyl alcohol which may contain minor amounts of polyvinyl acetate as commercially made. Water-soluble polyvinyl polymeric amides such as polyvinylpyrrolidone of suitable molecular weight may be employedalso.

In general, the amount of the soil-suspending agent (including mixtures thereof) is usually from about 0.1 to about 2% by weight in the liquid product. Various materials or mixtures may be employed which assist in maintaining the soil-suspending materials in suspension or dispersion in the liquid. Suitable mixtures of cellulosic compounds, or a mixture of a cellulosic compound with a vinyl polymer, or a mixture of a cellulosic compound with castor wax, or any combination thereof, may be employed.

The liquid detergent product is prepared in any suitable manner. The hydrotropic salts, the polyphosphate and the organic detergents are added successively in the form of powders, aqueous solutions or slurries to the aqueous medium. The alkylolamide and any waxy materials are preferably added in molten or liquid form with agitation to form a homogeneous product. The alcohol may be added at any stage or in combination with a detergent. The soil-suspending agent may be added in the form of an aqueous solution at any stage during the mixing operations. The temperature of admixture should be sufficient to dissolve or melt the ingredients and reasonably elevated temperature conditions such as up to about 200 F. may be employed as required.

Various other ingredients may be added as desired including compatible perfumes, coloring materials, corrosion or tarnish inhibitors, germicides, bleaching agents, optical bleaches or fluorescent dyes, viscosity modifiers or additional solvent materials, and the like.

The following examples are further illustrative of the nature of the present invention, and it will be understood Examples In the above formulation, the higher alkyl benzene sulfonate is a commercial mixture of the propylene tetramer and pentamer benzene sulfonates corresponding on the average to a tridecyl benzene sulfonate. The higher alkyl benzene sulfonate is listed on an active ingredient basis, but contains in addition about 1.6 parts of sodium sulfate in the formulation. The polyethoxamer sulfate material has an average of 5 moles ethylene oxide. The hydrotropic salt is listed on an active ingredient basis and is of purity. The xylene sulfonate comprises a mixture of the meta-, para-, and ortho-xylene sulfonates with some toluene sulfonate.

The above composition is a clear solution at room temperature having satisfactory cleansing power.

Examples 11-] V In the above formulations, the tridecyl benzene sulfonate is a commercial mixture as described in Example I and the polyethoxamer sulfate material has an average 'of 5 moles ethylene oxide. The alkylolainides and polyethoxamer sulfate have the lauryl and myristyl groups in a 70:30 ratio by weight. These liquids possess a high level of cleaning and foaming Power.

Example V Ingredients: Percent Sodium tridecyl benzene sulfonate 10 Sodium lauryl polyethoxamer sulfate (average of 5 ethylene oxide groups) 3 Lauric-myristic (70:30) isopropanolamide 2.5 Lauric-myristic (70:30) diethanolamide 2.5 Sodium xylene sulfonate (comm.) 8.6 Potassium pyrophosphate 15 Water Bal.

The product is a clear solution at room temperature having a cloud point below 38 F. with satisfactory cleansing properties in use.

Although the present invention has been described with reference to particular embodiments and examples, it will be apparent to those skilled in the art that variations and modifications can be substituted therefor without departing from the principles and true spirit of the invention.

Having thus described the invention, what is claimed is:

1. A homogeneous, pourable liquid detergent composition which consists essentially of about 10 to 18% by weight of a mixture of an alkali metal alkyl mononuclear aryl sulfonate detergent salt, said alkyl group having about 8 to 15 carbon atoms, an alkali metal alkyl polyethoxamer sulfate salt, said alkyl group having about 10 to 18 carbon atoms and said polyethoxamer sulfate having an average of about 2 to 15 moles of ethylene oxide, the ratio of said alkyl aryl sulfonate to polyethoxamer sulfate being from about 6.5 :l to about 1:4 by weight; a total of about 10 to 20% by weight of potassium polyphosphate, and about 6 to 12% by weight of a hydrotropic salt selected from the group consisting of sodium and potassium salts of xylene, toluene, ethyl benzene and isopropylbenzene sulfonate, n-arnyl and n-hexyl sulfate, and mixtures thereof, and the balance being substantially water.

2. A liquid detergent composition which consists essentially of about 10 to 18% by weight of a mixture of an alkali metal higher alkyl benzene sulfonate detergent, said higher alkyl group having about 8 to 15 carbon atoms, 'an alkali metal alkyl polyethoxamer sulfate salt having about to 18 carbon atoms in the alkyl group and an average of about 2 to moles of ethylene oxide, the ratio of said alkyl benzene sulfonate to polyethoxamer sulfate being from about 6.5 :1 to about 1:4 by weight; a total of about 10 to by Weight of water-soluble potassium polyphosphate, about 6 to 12% by weight of a hydrotropic salt selected from the group consisting of sodium and potassium salts of xylene, toluene, ethylbenzene and isopropylbenzene sulfonate, n-amyl and n-hexylsulfate, and mixtures thereof, about 2 to 10% by weight of a higher fatty acid alkylolamide having 8 to 18 carbons in the acyl radical and up to 3 carbon atoms in each alkylol group, and the balance being substantially water, the composition containing said ingredients forming in anaqueous solubilizing medium a homogeneous, pourable, clear liquid at room temperature.

3. A liquid detergent composition in accordance with claim 2 wherein said polyethoxamer sulfate salt has an average of about 3 to 8 moles of ethylene oxide.

4. A liquid detergent composition in accordance with claim 2 wherein said hydrotropic salt is potassium xylene sulfonate. V

5. A liquid detergent composition in accordance with claim 2 wherein said alkylolamide is selected from the group consisting of diethanolamides, monoethanolamides and isopropanolamides of fatty acids having 10 to 14 carbons in the acyl radical.

6. A liquid detergent composition which consists essentially of about 10 to 18% by weight of a mixture of an alkali metal higher alkyl benzene sulfonate detergent, said higher alkyl group having about 8 to 15 carbon atoms, an alkali metal alkyl polyethoxamer sulfate salt having about 12 to 14 carbon atoms in said alkyl group and an average of about 3 to about 8 moles of ethylene oxide, the ratio of said alkyl benzene sulfonate to polyethoxamer sulfate being from about 6.5:1 to about 1:4 by weight; about 10 to 20% by weight of water-soluble potassium polyphosphate, about 6 to 12% by Weight of a hydrotropic salt selected from the group consisting of sodium and potassium salts of xylene, toluene, ethylbenzene and isopropylbenzene sulfonate, n-amyl and n-hexyl sulfate, and mixtures thereof, about 2 to 10% by weight of a higher fatty acid alkylolamide having 8 to 18 carbons in the acyl radical and up to 3 carbon atoms in each alkylol group and the balance being substantially water, the composition containing said ingredients forming a homogeneous, pourable, clear liquid at room temperature.

7. A liquid detergent composition which consists essentially of about 10 to 18% by weight of a mixture of an alkali metal higher alkyl benzene sulfonate detergent, said higher alkyl group having about 8 to 15 carbon atoms, an alkali metal alkyl polyethoxamer sulfate salt material having about 12 to 14 carbon atoms in said alkyl group and an average of about 3 to about 8 moles of ethylene oxide, the ratio of said alkyl benzene sulfonate to polyethoxamer sulfate being greater than 1:1 and up to 6.5 :1 by weight; about 10 to 20% by weight of water-soluble potassium pyrophosphate, about 6 to 12% by weight of a hydrotropic salt selected from the group consisting of sodium and potassium salts of xylene, toluene, ethylbenzene and isopropylbenzene sulfonate, n-amyl and n-hexyl sulfate, and mixtures thereof about 4 to 3% by weight of a higher fatty acid alkylolamide having about 10 to 14 carbon atoms in the acyl group and up to 3 carbon atoms in each alkylol group, and the balance being substantially water, the composition containing said ingredients having a solids content of up to about by weight and forming a homogeneous, pourable, clear liquid at room temperature.

References Cited by the Examiner UNITED STATES PATENTS 2,877,187 3/1959 Henderson et al 252153 2,930,760 3/1960 Gebhardt 252 2,950,254 8/1960 Meinhard et al. 252-152 FOREIGN PATENTS 1,047,973 12/ 1958 Germany.

JULIUS GREENWALD, Primary Examiner. 

2. A LIQUID DETERGENT COMPOSITION WHICH CONSISTS ESSENTIALLY OF ABOUT 10 TO 18% BY WEIGHT OF A MIXTURE OF AN ALKALI METAL HIGHER ALKYL BENZENE SULFONATE DETERGENT, SAID HIGHER ALKYL GROUP HAVING ABOUT 8 TO 15 CARBON ATOMS, AN ALKALI METAL ALKYL POLYETHOXAMER SULFATE SALT HAVING ABOUT 10 TO 18 CARBON ATOMS IN THE ALKYL GROUP AND AN AVERAGE OF ABOUT 2 TO 15 MOLES OF ETHYLENE OXIDE, THE RATIO OF SAID ALKYL BENZENE SULFONATE TO POLYTHOXAMER SULFATE BEING FROM ABOUT 6.5:1 TO ABOUT 1:4 BY WEIGHT; A TOTAL OF ABOUT 10 TO 20% BY WEIGHT OF WATER-SOLUBLE POTASSIUM POLYPHOSPHATE, ABOUT 6 TO 12% BY WEIGHT OF A HYDROTROPIC SALT SELECTED FROM THE GROUP CONSISTING OF SODIUM AND POTASSIUM SALTS OF XYLENE, TOLUENE, ETHYLBENZENE AND ISOPROPYLBENZENE SULFONAT,E N-AMYL AND N-HEXYLSULFATE, AND MIXTURES THEREOF, ABOUT 2 TO 10% BY WEIGHT OF A HIGHER FATTY ACID ALKYLOLLAMIDE HAVING 8 TO 18 CARBON IN THE ACYL RADICAL AND UP TO 3 CARBON ATOMS IN EACH ALKYLOL GROUP, AND THE BALANCE BEING SUBSTANTIALLY WATER, THE COMPOSITION CONTAINING SAID INGREDIENTS FORMING IN AN AQUEOUS SOLUBILIZING MEDIUM A HOMOGENEOUS, POURABLE, CLEAR LIQUID AT ROOM TEMPERATURE. 